Unified Classical Thermodynamics: Primacy of Dissymmetry over Free Energy

Thermo Pub Date : 2024-07-19 DOI:10.3390/thermo4030017
Lin-Shu Wang
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Abstract

In thermodynamic theory, free energy (i.e., available energy) is the concept facilitating the combined applications of the theory’s two fundamental laws, the first and the second laws of thermodynamics. The critical step was taken by Kelvin, then by Helmholtz and Gibbs—that in natural processes, free energy dissipates spontaneously. With the formulation of the second law of entropy growth, this may be referred to as the dissymmetry proposition manifested in the spontaneous increase of system/environment entropy towards equilibrium. Because of Kelvin’s pre-entropy law formulation of free energy, our concept of free energy is still defined, within a framework on the premise of primacy of energy, as “body’s internal energy or enthalpy, subtracted by energy that is not available.” This primacy of energy is called into question because the driving force to cause a system’s change is the purview of the second law. This paper makes a case for an engineering thermodynamics framework, instead, to be based on the premise of the primacy of dissymmetry over free energy. With Gibbsian thermodynamics undergirded with dissymmetry proposition and engineering thermodynamics with a dissymmetry premise, the two branches of thermodynamics are unified to become classical thermodynamics.
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统一经典热力学:不对称高于自由能
在热力学理论中,自由能(即可用能量)是一个概念,它促进了热力学第一定律和第二定律这两个基本定律的综合应用。开尔文、亥姆霍兹和吉布斯先后迈出了关键的一步--在自然过程中,自由能会自发耗散。根据熵增第二定律的表述,这可以被称为不对称命题,表现为系统/环境熵自发增加以达到平衡。由于开尔文在熵定律之前对自由能的表述,我们对自由能的概念仍然是在能量至上的前提下,将其定义为 "身体的内能或焓,减去不可用的能量"。由于导致系统变化的驱动力属于第二定律的范畴,因此能量的首要地位受到质疑。本文提出了一个工程热力学框架,该框架应建立在不对称比自由能更重要的前提之上。吉布斯热力学以不对称命题为基础,工程热力学以不对称为前提,两个热力学分支统一成为经典热力学。
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